Detergent compositions containing maleic acid vinyl alcohol copolymers as builders

ABSTRACT

BUILDERS FOR DETERGENT AND CLEANING AGENTS. THE BUILDERS ARE COMPRISED OF WATER-SOLUBLE SATS OF COTELOMERS OR COPOLYMERS OF VIINYL ALCOHOL WITH MALEIC ACID.   D R A W I N G

1974 J. KANDLER ETAL 3,793,228

DETERGENT COMPOSITIONS CONTAINING MALEIC ACID VINYL I ALCOHOL COPQLYMERS AS BUILDERS Original Filed Sept. 16, 1970 2 Sheets-Sheet 1 Z W1C cleansir fiower Quotient 0.2 1.0 2.0 Builder Concentralion g'5u1fccoe AcliveSubsicmce: 0. fly/Lrlter 100% I Alkyleuysuy onale OJfiy/L L'for Pluronic C arm 1 2 VDyLALcokol/Maleaie; Molecular Proportion 1 1 Curve 2 S iyrene /Maleae Molecular Proporiion 2 Curve 3 1 Styrene /Ma:leae Molecular Proporiion 2.5-!

Feb. 19', 1974 KANDLER ETAL 3,793,228

DETERGENT COMPOSITIONS CONTAINING MALEIC ACID VINYL ALCOHOL COPOLYMERS AS BUILDERS Original Filed Sept 16, 1970 2 Sheets-Sheet 2 77 WA? Cleans'ug ower Quotient 0.2 1.0 2.0 Builder Curve 1: Vz'nylAlcokol/jllaleaie; Molecular Proportion 1:1 Curve 2 1 syr n /Maleaie; Molecularfiroporiion 2 Curve 3 SWrene/Malemfe; Molecalccrproporlzbn 2.5:]

, theIemuIsificatiOn of dirt par.

United States Patent O ice 3,793,228 r DETERGENT COMPOSITIONS "CONTAININ G MALEIC ACID VINYL ALCOHOLCOPOLY MERS AS BUILDERS l Joachim Kandler and Karl Merkenich, Cologne, Herbert Landgraber, Elferen, near Cologne, Klaus Henning, Hurth, near Cologne, and Alfred Kohlkamp, Hofheim, Taunus, Germany, assignors to Knapsack Aktiengesellschaft, Knapsack, near Cologne, Germany Original application Sept. 16, 1970, S'er. No. 72,705, now abandoned. Divided and this application Oct. 24, 1972, Ser. No. 299,821 Claims priority, application Germany, Oct. 8, 1969,

P 19 50 702.9. a Int. Cl. C02]: 5/06; C08f /02; Clld 3/,20 US. Cl. 252-541 g D 7 ABSTRA or or I'Hli ius crlosula Builders for detergent and cleaning agents. The builders are comprised of water-soluble salts of cotelomers or copolymers of vinyl alcohol with maleic acid.

This application'is a division pr application Ser. No. 72,705, filed Sept. 16,1970,:nowabandoned.

The present invention provides builders foridetcrgen't and cleaning agents, the builders comprising organic polymer compounds.

It has already been reported that the cleaning power of soaps and synthetic detergents in detergent and cleaning compositions can be improved by means of certain addends. These cleaning intensifiers are termed builders. Detergent and cleaning compositions having such builders therein are more effective, yet less costly than corresponding formulations which are free from builders.

The mechanism andthe details of the builder effect have not yet been fully described. Vital to the function of thebuilder is a pluralityof processes comprising, for example; the stabilization ofpigment dirt suspensions;

V y s; theeffect onlthefs'urface and interfacial properties" (if aqueous surfactant" solutions; the solubilization of waterinsoluble ingredients of the cleaning bath; the pepti zati'on of agglomerat'e d dirt; the neutralization of acid-substances; and the inactivation of mineral matter in the cleaning bath.

To determine materials for use as a builder, it is good practice to test their behavior and efficiency in washing or cleaning operations, to ensure the qualitative and quantitative determination of all factors that make their contribution to the builder effect.

Classical builders comprise water-soluble inorganic alkali metal salts, such as alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates, and silicates.

While a plurality of materials have been suggested for use as builders, the fact remains that linear condensed phosphates or polyphosphates, more particularly pentasodium triphosphate or sodium tripolyphosphate, are almost exclusively used as the builders in customary detergent and cleaning compositions, having up to substantially 50 Weight percent builder therein. Despite the many advantages which polyphosphate builders offer over further conventional builders, they have been found during their long years practical use to also have some disadvantages.

In all polyphosphates, the PO-P bond, which is formed by dehydration, is relatively easy to split hydrolytically. This results in the formation of decomposition products, such as metaphosphates or orthophosphate of reduced efficiency, particularly in the case of liquid detergent and cleaning compositions, but also in the spray process. In addition thereto, liquid detergent formulations may be Claims 3,793,228 Patented Feb. 19, 1974 1 rendered turbid, or precipitation may occur therein, which is undesirable.

The considerably increased consumption of phosphatecontaining detergent and cleaning agents both for domestic and industrial purposes has also effected an increase in the phosphate content of natural waters receiving phosphate salt-containing waste water. On discussing the entrophication'of waters, which has been found to occur at constantly increasing rates for some years, the nitrates and p'hosphates'have recently been held to have properties that are" able under certain conditions to promote the growth of certain alga species, and thereby to make their contribution to the eutrophication of water. Even though it is impossible for the time being definitely to clarify this problem, his highly desirable to have potential substitutes for the builders, namely tripolyphosphate, that find widealso contain a good deal of nitrogen and phosphorus eme. In U.S. v Pat. 3,308,067, it has been suggested that watersoluble alkali metal, ammonium and substituted ammonium salts of homopolymers and copolymers of aliphaticpolycarboxylic acids be used as builders in detergent and cleaning compositions. The comonomers include primarly short chain olefins and unsaturated carboxylic acids. Representatives of these builders, which are termed polyelectrolyte builders, include for example, the sodium salt of polymaleic acid or copolymers of propylene or styrene with maleic acid. These builders either have no satisfactory builder properties or are too costly for mass production.

The present invention now unexpectedly provides watersoluble'salts of cotelomers or copolymers of vinyl alcohol withymaleic-acid, which can be used with particular advantage as buildersin detergent and cleaning compositions. The. builders suggested to be used in accordance the qfilalifyagndquafificatfifi of indiifaua'l withthe'present invention preferably have the following general formula? [M] ii 1!! l (1-m) O= E JJ=0 Me J Me m n in which m is the maleic acid fraction in the copolymer, of at most about 55 mole percent,

Me stands for an alkali metal or ammonium ion, and

n is a whole number within a range of which the lower limit is 3 and of which the upper limit is defined by the solubility of the polymer in water,

In accordance with a further feature of the present invention, the copolymer builders have a preferred molecular weight of between 1,500 and 3,000. In accordance with a still further feature of the present invention, the maleic acid fraction in the copolymer or cotelomer should preferably be limited to a value of between about 25 and 50 mol percent.

To produce detergent and cleaning compositions, it is possible to introduce the copolymer builders of the present invention into conventional detergent and cleaning agent formulations, such as those which are based on ionactive and/ or non-ionic surfactants, and which may op- 3 tionally be used in combination with further addends In accordance with the present invention, the builder is generally used in a proportion of between about 10 and 80 Weight percent, preferably between about 15 and 60 weight percent, based on the drysubstance of the detergent and cleaning agent. In addition to a water-soluble copolymer of vinyl alcohol and maleic acid, the detergent and cleaning agents may contain an alkali metal polyphosphate as a further builder. Detergent and cleaning compositions prepared in accordance with the present invention give a pH-value of between 8 and 12 in the aqueous medium of the wash bath. I

The addends, which may be present together with the ion-active and/or non-ionic surfactants in the detergent formulation, comprise substances, such as sodium silicate, magnesium silicate, sodium sulfate, sodiumf'perborate, optical brighteners, carboxymethyl cellulose and/ or enzymes, for example.

The builders of the present invention are produced in conventional manner, for example, by subjecting a copolymer or telomer of maleic anhydride and vinyl acetate to saponification by means of a sodium hydroxide solution.

The properties of the builders of the persent invention can be evaluated, for example, in dispersing tests. Starting with an aqueous suspension, which contained either hydrophilic particles, such as iron (III) oxide, or hydrophobic particles, for example graphite particles, it was possible by the addition of the builders of the present invention to produce stable dispersions. This is demonstrated in the table hereinafter. As results from the tabulated test results, the builder substances of the present invention can be said to have the properties required of a builder. On comparing Table 1 with Table 2, it will readily be seen that hydrophilic dirt particles are particularly well dispersed by a vinyl alcohol/maleate cotelomer. The reason for this is that both the settling rate and sedimentation volume are smaller than in a comparative test made with the use of a styrene/maleate cotelomer as the builder. As compared with conventional alkali metal tripolyphosphate builders, those of the present invention have the advantage of dispersing hydrophobic dirt, whereas the alkali metal tripolyphosphates fail to produce such effect.

EXAMPLE 1 The sodium salt of a vinyl alcohol/melic acid copolymer was tested as to its dispersing effect in an aqueous suspension of 4 weight percent graphite powder at various pH-values, and the eifect produced was compared with that produced by a conventional styrene/maleic acid copolymer builder, in a corresponding suspension. The settling time of the graphite particles in 25 cc. mixing cylinders, and the volume of sedimentation were determined in each case as an index of the dispersing effect. The builder was used in the suspension in a concentration of 0.1 weight percent, based on the aqueous solution. Th results obtained are summarized in Table 1 below.

TABLE 1 Volume of sedi- Settling time in mentation in hours cubic centimeters Builder pH 8 pH 10 pH 8 pH 10 A 21 21 1. 9 1. 8 B 2-1 24 1. 9 1. 8 C. 20 20 3. 3. 4

ple 1 save that iron (III) oxide powder with a particle 'f' size of less than 0.058 mm. was substituted for the graphite powder. The test results are indicated in Table N o'rE.A=Styrene/maleate; molar ratio=2:1; molecular weight= 1,330. B=Styrene/maleate; molar ratio=2.5:1; molecular weight=1,544. C=V1nyl alcohol/maleate; molar ratio=1z 1; molecular weight=1,940.

. EXAMPLE 3 Wash tests weremade to determine the cleansing power quotients of wash liquors which for a constant concentration of surface active substance contained varying proportions of builder (invention), and the test results obtained were graphically plotted in FIG. 1 of the accompanying graphs (curve 1). Analogous wash tests with the use'of conventional builders, such as styrene/maleate, were made for the purpose of comparison.

The cleansing power quotients are also graphically plotted in FIG. 1, curves 2 and 3. I

The wash tests were made on standard cotton fabrics soiled with Krefeld dirt in a Launder-O-meter at a wash bath temperature of -C. Standard fabrics soiled with Krefeld dirt have been defined by Kurt Lindner in the book entitled: Tenside, Textilhilfsmittel-Waschrohstotfe, Wissenschaftl. Verlagsgesellschaft Stuttgart (1964), volume II, page 1837.

The wash water had a hardness of 20 (German degrees of hardness) and a pH of 10. The wash period was 30 minutes and the bath ratio, expressed by the ratio of material to be washed in kg. to wash liquor in liter was 1:50, and the wash operation was carried out in the presence of 10 steel balls. The wash liquor contained a alkylaryl sulfonate as a surface-active substance as well as Pluronic which is a non-ionic polyoxypropylene glykol.

After the prescribed wash time, the standard cotton fabric was rinsed, once hot and once cold, and its degree of whiteness was then determined using an Elrepho remission photometer (a produce of Zeiss) and a filter R 55. Based on the test result obtained, the cleansing power quotient was calculated along the following formula:

Percent WG Peroent WG 100 Percent WK m in which Percent WK=Percent cleansing power, Percent WG =Percent whiteness of washed fabric,

Percent WG =Percent whiteness of unwashed fabric, Percent WG =Percent whiteness of unsoiled fabric.

As can be seen from curves 1, 2 and 3 shown in FIG. 1, more cleansing power is imparted to the wash liquor by the builder of the present invention, to which belongs curve 1, than by conventional builders, to which belong curves 2 and 3. i

EXAMPLE 4 The procedure was the same as that described in Example 3, save that the wash liquor contained the builder and a fully active detergentcomposed of As can be seen from curve 1- in FIG. 2, the builder of the present invention was again found to distinguish Fl] it Ill (5H m =0 )=O 0M0 0Me m n in which m is the maleic acid fraction in the copolymer and is from about 25 to 55 mole percent,

Me stands for an alkali metal or ammonium ion, and

n is a whole number with a range of which the lower limit is 3 and of which the upper limit is defined by the solubility of the polymer in water.

2. A detergent composition as claimed in claim 1 wherein the copolymer of vinyl alcohol and maleic acid is present in an amount between about 15 and 60 weight percent based on the dry weight of the detergent composition.

3. A detergent composition in accordance with claim 1, wherein the copolymer has a molecular weight of between 1,500 and 3,000.

4. A detergent composition according to claim 1 wherein maleic acid constitutes mole percent of the copolymer.

5. A detergent composition in accordance with claim 1, further containing an effective amount of an alkali metal polyphosphate as a supplemental builder.

6. A detergent composition according to claim 1, producing a pH value of between 8 and 12 in an aqueous wash or cleaning liquor.

7. A detergent composition in accordance with claim 1, further containing a minor amount of at least one material selected from the group consisting of sodium silicate, magnesium silicate and sodium sulfate.

References Cited UNITED STATES PATENTS 3,700,599 10/1972 Mizuno 252-99 3,686,145 8/1972 Haschke 260-67 U 3,676,373 7/1972 Paviak 252-531 3,627,686 12/1971 Sabatelli 252-527 3,579,455 5/1971 Sabatelli 252- 3,308,067 3/1967 Diehl 252-89 X 3,284,364 11/1966 Siegele 252-132 2,306,071 12/1942 McNally 260-78 2,047,398 7/ 1936 Voss 260-2 LEON D. ROSDOL, Primary Examiner D. L. ALBRECHT, Assistant Examiner U.S. Cl. X.R.

252-89, 132, 135, 180, 523, Digests 2, 11; 260-785 R 

